WO2012158600A1 - Fabrication et applications de métal de silicium - Google Patents

Fabrication et applications de métal de silicium Download PDF

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Publication number
WO2012158600A1
WO2012158600A1 PCT/US2012/037740 US2012037740W WO2012158600A1 WO 2012158600 A1 WO2012158600 A1 WO 2012158600A1 US 2012037740 W US2012037740 W US 2012037740W WO 2012158600 A1 WO2012158600 A1 WO 2012158600A1
Authority
WO
WIPO (PCT)
Prior art keywords
silicon metal
metal
silicon
sodium
purity
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2012/037740
Other languages
English (en)
Inventor
Andrew Matheson
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Boston Silicon Materials LLC
Original Assignee
Boston Silicon Materials LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Boston Silicon Materials LLC filed Critical Boston Silicon Materials LLC
Priority to EP12785151.7A priority Critical patent/EP2709952A4/fr
Priority to CN201280023994.8A priority patent/CN103702937A/zh
Publication of WO2012158600A1 publication Critical patent/WO2012158600A1/fr
Priority to US14/078,927 priority patent/US20140072498A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/029—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition of monosilane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/04—Production of hydrogen; Production of gaseous mixtures containing hydrogen by decomposition of inorganic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This invention relates to the production of high purity silicon metal.
  • Silicon metal is useful both as the basis for semiconductors, and as the key constituent of the majority of photovoltaic (PV) cells. Silicon metal for these applications is required to be extremely pure, typically 99.9999% (6N) or higher purity for PV cells, and typically 9N or higher purity for semiconductor applications. Silicon of this purity is usually manufactured in large and extremely capital-intensive facilities, in which gas phase chemical vapor deposition is used to build up high purity silicon metal from silicon-containing gases. The two main gases used are trichlorosilane (S1HCI 3 ), and silicon hydride or silane (SiH 4 ).
  • S1HCI 3 trichlorosilane
  • SiH 4 silicon hydride or silane
  • the invention relates to the production of silicon metal, for which the production process is particularly well-suited and also economically advantageous.
  • One preferred process of the present invention comprises: introducing silane gas into a reactor vessel containing a reductant,
  • an alkali or alkaline earth metal or combinations thereof preferentially an alkali or alkaline earth metal or combinations thereof, and most preferentially sodium metal, potassium metal, and alloys thereof, at a temperature sufficient to ensure the reductant is liquid;
  • reaction product a mixture of silicon metal and excess reductant
  • the metal thus produced is in the form of a metal powder or extended aggregate structure with internal porosity.
  • the particle size produced by this process is controlled by a number of factors, including the reaction temperature, the relative concentrations of the reagents, and the melting point of silicon metal.
  • the metal produced by this methodology can be densified by melting to produce silicon of high purity.
  • silicon of a purity suitable for use in photovoltaic cells and even semiconductor devices can be produced.
  • all the processes described herein can be accomplished using a gas phase reductant in place of the preferred liquid phase reductant.
  • One embodiment of the present invention is a process to convert silane gas (SiH 4 ) to silicon metal by a liquid or vapor comprising reacting the silane gas with one or more alkali or alkaline earth metals.
  • the alkali or alkaline earth metals comprise either sodium, or potassium, or alloys thereof.
  • the alkali or alkaline earth metal is captured and recovered for reuse in the process.
  • the reaction product of this process comprises silicon metal, and at least 0.1% metallic sodium. In certain embodiments, the reaction product of this process comprises silicon metal, and at least 1% metallic sodium. Yet another reaction product is hydrogen gas. The hydrogen generated in the process may be recovered and used in commercial applications, if desired.
  • the silicon metal after removal of the excess sodium, has a purity of at least 99.9%. In certain embodiments, the silicon metal, after removal of the excess sodium, has a purity of at least 99.99%. In certain
  • the silicon metal, after removal of the excess sodium has a purity of at least 99.999%. In certain embodiments, the silicon metal, after removal of the excess sodium, has a purity of at least 99.9999%. In certain embodiments, the silicon metal, after removal of the excess sodium, has a purity of at least 99.99999%. In certain embodiments, the silicon metal has a primary particle diameter of less than 1 micron.
  • Silicon metal having a purity as provided herein may be employed in a photovoltaic device. Silicon metal having a purity as provided herein may be employed in a semiconductor device. Silicon metal having a purity as provided herein may be employed in a sputtering target.
  • silane can be injected into molten reductant, and reduced therein to silicon metal in particulate form.
  • the typical size of the silicon particle is a function of the temperature of the reaction, the flow rates of the reagents, and the diffusion characteristics of silicon. By careful control of the reaction conditions, one can select for a range of typical metal particle sizes.
  • the surface area of the metal is related to the particle size, and the surface area of the metal particle determines many important physical characteristics of the metal in commercial applications. Particle sizes are summarized in the following table:
  • reaction product can be removed from the reactor and then be treated to remove the reductant and any reductant hydride, or can first be treated before removing the silicon metal.
  • Silane gas is injected into a reactor vessel containing molten sodium and is allowed to flow until the evolved hydrogen indicates the presence of unreacted silane gas, at which point the flow of silane is stopped.
  • the reactor vessel is then heated to a temperature of at least 300 degrees centigrade and a partial vacuum of 100 torr or less is applied to the vessel to remove any hydrogen produced by the breakdown of sodium hydride.
  • the temperature is raised to above the boiling point of sodium, and the sodium vapor is removed and condensed to recover the sodium.
  • This step can be accomplished at lower temperatures by the application of a partial or full vacuum (100 torr or less) to the reactor vessel.
  • the silicon metal can be removed from the reactor vessel for further processing or sale, or else can be heated to above the melting point of silicon in order to produce a dense solid of silicon.
  • the sodium is not consumed in the reaction, instead acting as a catalyst to promote the decomposition of silane gas, and can be re-used with obvious beneficial impact on the economics of the process.
  • EXAMPLE 2 Silane gas is injected into a stream of sodium-potassium alloy (NaK) and decomposes to silicon, hydrogen, and potentially some hydrides of sodium and potassium.
  • NaK sodium-potassium alloy
  • the solid silicon is removed from the NaK stream by filtration. Hydrogen gas produced in the decomposition of silane is vented from the NaK stream and is recovered for disposal, sale or other use. The reactor products are captured without exposure to air or moisture.
  • reaction products are then heated to break down any sodium or potassium hydrides into hydrogen and either sodium or potassium, and the hydrogen is captured for sale, use or disposal.
  • This step can be facilitated by the application of a full or partial vacuum of 100 torr or less.
  • reaction product is heated to a temperature sufficient to remove as a vapor the NaK present with the silicon.
  • a full or partial vacuum of 100 torr or less reduces the temperature required to remove the excess NaK.
  • the silicon metal can be taken for further processing or sale, or else can be heated to above the melting point of silicon in order to produce a dense solid of silicon.
  • the NaK is not consumed in the reaction, instead acting as a catalyst to promote the decomposition of silane gas, and can be re-used with obvious beneficial impact on the economics of the process.
  • the removal of the sodium or the NaK can be achieved by use of a non-aqueous solvent (for example, ammonia, alcohols such as methanol, ethanol etc, and other polar solvents) that does not dissolve the silicon metal.
  • a non-aqueous solvent for example, ammonia, alcohols such as methanol, ethanol etc, and other polar solvents
  • the dissolved sodium or NaK can then be removed from the solvent for recycling, and the solvent can be recycled also.
  • the silicon metal can then be recovered as described in Examples 1 and 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Silicon Compounds (AREA)

Abstract

La présente invention concerne un procédé de fabrication qui utilise la réduction en phase liquide d'hydrure de silicium, pour produire du métal de silicium. Le travail en phase liquide permet une conception d'usine plus compacte et permet d'atteindre des coûts d'investissement significativement plus faibles.
PCT/US2012/037740 2011-05-16 2012-05-14 Fabrication et applications de métal de silicium Ceased WO2012158600A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP12785151.7A EP2709952A4 (fr) 2011-05-16 2012-05-14 Fabrication et applications de métal de silicium
CN201280023994.8A CN103702937A (zh) 2011-05-16 2012-05-14 金属硅的生产和应用
US14/078,927 US20140072498A1 (en) 2011-05-16 2013-11-13 Manufacturing and Applications of Silicon Metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201161486429P 2011-05-16 2011-05-16
US61/486,429 2011-05-16

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US14/078,927 Continuation US20140072498A1 (en) 2011-05-16 2013-11-13 Manufacturing and Applications of Silicon Metal

Publications (1)

Publication Number Publication Date
WO2012158600A1 true WO2012158600A1 (fr) 2012-11-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2012/037740 Ceased WO2012158600A1 (fr) 2011-05-16 2012-05-14 Fabrication et applications de métal de silicium

Country Status (4)

Country Link
US (1) US20140072498A1 (fr)
EP (1) EP2709952A4 (fr)
CN (1) CN103702937A (fr)
WO (1) WO2012158600A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117295681A (zh) * 2021-03-12 2023-12-26 尼古拉斯·乌戈林 通过液态碱金属合金中金属氢化物颗粒的悬浮液来储存和生产二氢

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118387878A (zh) * 2024-04-16 2024-07-26 中南大学 一种纳米硅的制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4756896A (en) * 1985-03-11 1988-07-12 Kemira Oy Method of preparing silicon
US20100158782A1 (en) * 2008-08-25 2010-06-24 Orion Laboratories, Llc Magnesiothermic Methods Of Producing High-Purity Silicon
US20100154475A1 (en) * 2007-08-01 2010-06-24 Andrew Matheson Process for the production of high purity elemental silicon
US20100215563A1 (en) * 2007-08-29 2010-08-26 Toshiharu Yambayashi Method for producing silicon

Family Cites Families (9)

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Publication number Priority date Publication date Assignee Title
NL134280C (fr) * 1959-05-13
US4265859A (en) * 1978-05-31 1981-05-05 Energy Materials Corporation Apparatus for producing semiconductor grade silicon and replenishing the melt of a crystal growth system
US4239740A (en) * 1979-05-25 1980-12-16 Westinghouse Electric Corp. Production of high purity silicon by a heterogeneous arc heater reduction
US4343772A (en) * 1980-02-29 1982-08-10 Nasa Thermal reactor
US5021221A (en) * 1980-10-20 1991-06-04 Aero Chem Research Lab., Inc. Apparatus for producing high purity silicon from flames of sodium and silicon tetrachloride
CA1198581A (fr) * 1980-10-20 1985-12-31 Robert K. Gould Methode et dispositif de production de silicone extra- pur et partir des flammes de sodium et de tetrachlorure de silicium
WO2004016823A1 (fr) * 2002-08-12 2004-02-26 Nikko Materials Company, Limited Substrat de silicium ou cible de pulverisation en silicium et procede de fabrication correspondant
CN1935649A (zh) * 2006-09-25 2007-03-28 哈尔滨工业大学 采用无氯烷氧基硅烷制备多晶硅的方法
CN102365234A (zh) * 2009-03-20 2012-02-29 波士顿硅材料有限公司 制造光伏级硅金属的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4756896A (en) * 1985-03-11 1988-07-12 Kemira Oy Method of preparing silicon
US20100154475A1 (en) * 2007-08-01 2010-06-24 Andrew Matheson Process for the production of high purity elemental silicon
US20100215563A1 (en) * 2007-08-29 2010-08-26 Toshiharu Yambayashi Method for producing silicon
US20100158782A1 (en) * 2008-08-25 2010-06-24 Orion Laboratories, Llc Magnesiothermic Methods Of Producing High-Purity Silicon

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP2709952A4 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117295681A (zh) * 2021-03-12 2023-12-26 尼古拉斯·乌戈林 通过液态碱金属合金中金属氢化物颗粒的悬浮液来储存和生产二氢

Also Published As

Publication number Publication date
CN103702937A (zh) 2014-04-02
EP2709952A1 (fr) 2014-03-26
US20140072498A1 (en) 2014-03-13
EP2709952A4 (fr) 2014-12-10

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